The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule

S.L. Hinchley, H.E. Robertson, K.B. Borisenko, A.R. Turner, B. Johnston, D.W.H. Rankin, M. Ahmadian, J.N. Jonesc, A.H. Cowley

Research output: Contribution to journalArticle

108 Citations (Scopus)

Abstract

The molecular structure of tetra-tert-butyldiphosphine has been determined in the gas phase by electron diffraction using the new DYNAMITE method and in the crystalline phase by X-ray diffraction. Ab initio methods were employed to gain a greater understanding of the structural preferences of this molecule in the gas phase, and to determine the intrinsic P–P bond energy, using recently described methods. Although the P–P bond is relatively long [GED 226.4(8) pm; X-ray 223.4(1) pm] and the dissociation energy is computed to be correspondingly small (150.6 kJ mol−1), the intrinsic energy of this bond (258.2 kJ mol−1) is normal for a diphosphine. The gaseous data were refined using the new Edinburgh structure refinement program ed@ed, which is described in detail. The molecular structure of gaseous P2But4 is compared to that of the isoelectronic 1,1,2,2-tetra-tert-butyldisilane. The molecules adopt a conformation with C2 symmetry. The P–P–C angles returned from the gas electron diffraction refinement are 118.8(6) and 98.9(6)°, a difference of 20°, whilst the C–P–C angle is 110.3(8)°. The corresponding parameters in the crystal are 120.9(1), 99.5(1) and 109.5(1)°. There are also large deformations within the tert-butyl groups, making the DYNAMITE analysis for this molecule extremely important.
LanguageEnglish
Pages2469-2476
Number of pages8
JournalDalton Transactions
Volume16
DOIs
Publication statusPublished - 2004

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Molecular structure
Electron diffraction
Molecules
Gases
Conformations
Crystalline materials
X ray diffraction
X rays
Crystals

Keywords

  • tetra-tert-butyldiphosphine
  • X-ray diffraction
  • DYNAMITE analysis

Cite this

Hinchley, S. L., Robertson, H. E., Borisenko, K. B., Turner, A. R., Johnston, B., Rankin, D. W. H., ... Cowley, A. H. (2004). The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule. Dalton Transactions, 16, 2469-2476. https://doi.org/10.1039/B407908F
Hinchley, S.L. ; Robertson, H.E. ; Borisenko, K.B. ; Turner, A.R. ; Johnston, B. ; Rankin, D.W.H. ; Ahmadian, M. ; Jonesc, J.N. ; Cowley, A.H. / The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule. In: Dalton Transactions. 2004 ; Vol. 16. pp. 2469-2476.
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Hinchley, SL, Robertson, HE, Borisenko, KB, Turner, AR, Johnston, B, Rankin, DWH, Ahmadian, M, Jonesc, JN & Cowley, AH 2004, 'The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule' Dalton Transactions, vol. 16, pp. 2469-2476. https://doi.org/10.1039/B407908F

The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule. / Hinchley, S.L.; Robertson, H.E.; Borisenko, K.B.; Turner, A.R.; Johnston, B.; Rankin, D.W.H.; Ahmadian, M.; Jonesc, J.N.; Cowley, A.H.

In: Dalton Transactions, Vol. 16, 2004, p. 2469-2476.

Research output: Contribution to journalArticle

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T1 - The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule

AU - Hinchley, S.L.

AU - Robertson, H.E.

AU - Borisenko, K.B.

AU - Turner, A.R.

AU - Johnston, B.

AU - Rankin, D.W.H.

AU - Ahmadian, M.

AU - Jonesc, J.N.

AU - Cowley, A.H.

PY - 2004

Y1 - 2004

N2 - The molecular structure of tetra-tert-butyldiphosphine has been determined in the gas phase by electron diffraction using the new DYNAMITE method and in the crystalline phase by X-ray diffraction. Ab initio methods were employed to gain a greater understanding of the structural preferences of this molecule in the gas phase, and to determine the intrinsic P–P bond energy, using recently described methods. Although the P–P bond is relatively long [GED 226.4(8) pm; X-ray 223.4(1) pm] and the dissociation energy is computed to be correspondingly small (150.6 kJ mol−1), the intrinsic energy of this bond (258.2 kJ mol−1) is normal for a diphosphine. The gaseous data were refined using the new Edinburgh structure refinement program ed@ed, which is described in detail. The molecular structure of gaseous P2But4 is compared to that of the isoelectronic 1,1,2,2-tetra-tert-butyldisilane. The molecules adopt a conformation with C2 symmetry. The P–P–C angles returned from the gas electron diffraction refinement are 118.8(6) and 98.9(6)°, a difference of 20°, whilst the C–P–C angle is 110.3(8)°. The corresponding parameters in the crystal are 120.9(1), 99.5(1) and 109.5(1)°. There are also large deformations within the tert-butyl groups, making the DYNAMITE analysis for this molecule extremely important.

AB - The molecular structure of tetra-tert-butyldiphosphine has been determined in the gas phase by electron diffraction using the new DYNAMITE method and in the crystalline phase by X-ray diffraction. Ab initio methods were employed to gain a greater understanding of the structural preferences of this molecule in the gas phase, and to determine the intrinsic P–P bond energy, using recently described methods. Although the P–P bond is relatively long [GED 226.4(8) pm; X-ray 223.4(1) pm] and the dissociation energy is computed to be correspondingly small (150.6 kJ mol−1), the intrinsic energy of this bond (258.2 kJ mol−1) is normal for a diphosphine. The gaseous data were refined using the new Edinburgh structure refinement program ed@ed, which is described in detail. The molecular structure of gaseous P2But4 is compared to that of the isoelectronic 1,1,2,2-tetra-tert-butyldisilane. The molecules adopt a conformation with C2 symmetry. The P–P–C angles returned from the gas electron diffraction refinement are 118.8(6) and 98.9(6)°, a difference of 20°, whilst the C–P–C angle is 110.3(8)°. The corresponding parameters in the crystal are 120.9(1), 99.5(1) and 109.5(1)°. There are also large deformations within the tert-butyl groups, making the DYNAMITE analysis for this molecule extremely important.

KW - tetra-tert-butyldiphosphine

KW - X-ray diffraction

KW - DYNAMITE analysis

U2 - 10.1039/B407908F

DO - 10.1039/B407908F

M3 - Article

VL - 16

SP - 2469

EP - 2476

JO - Dalton Transactions

T2 - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

ER -